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H
N
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H
N
Methanol
2 KOH
2
O-
OH
L-proline
K+
L-Potassium Prolinate
H
N
M e th a n o l
2 KOH
+ 2
2
O
OH
H 2N
H 2O
P o ta ss iu m p ro lin a te
L -p ro lin e
NH
CH
CH
H
N
O
+
M C l 2 .X H 2 O
O
CH
P o ta s s i u m p r o l i n a t e
Methanol
tr i m e t h o p r i m
NH
O
N
H 2N
CH
OH
M
NH
O
CH
H
N
CH
O
O
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in low range (3.32 to 19.6) -1 cm2 mol-1 supporting their non-electrolytic behavior[13]. The electrical
conductivity of these complexes found in the order:
Co > Cu > Ni > > Hg > Zn> Cd. Insolubility of these complexes in water and there non-electrolytic
nature provide sufficient evidence for covalence of the ligands.[13]
The atomic absorption measurements (Table-1) for all complexes gave approximated values for
theoretical values .The analysis data (Table-1) of metal complexes are consistent with their general formulation
as 1:2:1, mixed ligand complexes of the type [M (Pro)2(TMP)].The test for chloride ion with AgNO3 solution
was negative (Nil%) indicating that there is no chloride ion outside the coordination sphere of the central metal
[14],
Fourier-transform infrared spectra and m[of coordination :
The relevant vibration bands of the free ligands and the complexes are in the region 4004000cm1[15-16].
Comparative study of IR spectra of the mixed ligand complexes with ligand reveals that several peaks are shifted,
vanished or have newly appeared. The FT-IR spectra assignment off free ligand (L-proline), was summarized
in (Table 2) , and (Trimethoprim),was summarized in Table (3).The important IR peaks of the complexes are
given in (Table 4) . As regards the chelation of amino acid such , L-proline is evidently present in its zwitterionic
form and, therefore, the N-H moiety must be protonated, generating a NH2 + group whereas the acid group
remains in the anionic COO- form , Scheme (3) and the IR spectra of these cannot be compared entirely with
those of metal complexes as amino acids in metal complexes do not exist as zwitterions.[17,18] .
HO
_O
N
H
+
NH2
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complexes also showed new low intensity bands non-ligand band in the region 430-460cm-1 and 510-520cm1, which could be assigned to (M-O) and (M-N) modes respectively [6,21]. The region related to the CH and
CH2 stretching vibrations is very reach in bands , Most of the deformational modes were found in similar ranges
as in the free ligand. [20,21].OCH3 aromatic groups did not show any strong changes. New bands of weak
intensity observed in the regions around (524-590) cm-1and (416-482) cm-1 may be ascribed to M-N and M-O
vibrations, respectively [11, 21 ].It may be noted that, these vibrational bands are absent in the spectra of the
ligands .All the complexes are in agreement with octahedral geometry as proposed .[17,19]. Trimethoprim
complexes of coordination of the metal to the ligands is through the nitrogen of the pyrimidine group
Table (1): Some physical properties of the ligands and their complexes
35
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3-5- The ultra violet visible spectra and Magnetic measurements for the mixed- ligand :
Magnetic moments eff ( B) of each of the complexes are given in Table ( 5). These values suggest octahedral
geometry which is in good agreement with data of electronic transition [7,20].
UV/Visible spectra of the ligands
The electronic spectral data of the free ligands TMP and L-proline and their complexes are summarized in
table-5. The u. v- vis spectrum of TMP in DMSO solvent appeared a high intense absorption band at (257nm)
(38910cm-1) ( max=2431 molar1.cm-1). is attributed to [ */n* (overlap of the two peaks)aromatic ring
and (C=N) of the pyrimidine group] transitions .The electronic absorption spectrum of the L- Proline showed
three band at 240,284 and 349 nm.the first one may be assigned to intraligand * transition, where as the
second and third band may be assigned to the n* transition of the heterocyclic and COO- groups [nnn]. It is
found that these bands were shifted to lower energy on complexation , [22.24]
UV/Visible spectra of the metal complexes [M(Pro)2(TMP)(H2O)] complexes (1 to 6) :
[Co(Pro)2(TMP) (H2O)] complex (1)
The spectrum of the complex [Co(Pro)2(TMP)] shows two absorption bands at (275nm)(36363 cm-1)( max
=1995 molar-1 .cm-1), attributed to the charge transfer transition and at (774nm)(12919 cm-1)( max =9 molar1
.cm-1) attributed to the 4T1g(F) 4T2g(F) suggesting octahedral geometry of this complex [23,24].
[Ni (Pro)2(TMP) (H2O)] complex (2)
T he spectrum of the [Ni (Pro)2(TMP)(H2O)]complex shows two absorption bands at (274nm)(36493cm-1)(
max =1917 molar-1 .cm-1 ) attributed to the charge transfer transition and at (882nm)(11337 cm-1)( max =3
molar-1 .cm-1) attributed to 3A2g 3T2g suggesting octahedral geometry of this complex [ 23,24].
[Cu (Pro)2(TMP)(H2O)]complex (3)
The electronic absorption spectrum for [Cu (Pro)2(TMP)(H2O)]complex shows three absorption band at about
12224 cm-1 36363 cm-1 but they are overlapped. Because, octahedral complexes of Cu(II) are observable
distorted by Jahn-Teller effect and the structure of complex is to name distorted octahedral. It was to taken notice
of top of the peak as absorption band and dd transition at about (798nm)(12533cm-1) ( max =14 molar-1 .cm-1)
and (818nm)(12224cm-1) ( max =10 molar-1 .cm-1) may be due to due to 2Eg 2T2g transition, [ 19-.20] and
the uv-visible peak corresponding to the *transitions in the ligands were observed at(275nm)
(36363cm-1)(max=1995molar-1.cm-1) attributed to the charge transfer transition (CT).[22,23].
[Zn(Pro)2(TMP)(H2O)]complex(4),[Cd(Pro)2(TMP)(H2O)](5)and[Hg(Pro)2(TMP)(H2O)](6)complexes:
The Zn(II), Cd (II) and Hg (II) complexes table (5) showed diamagnetic as expected from their electronic
configuration and did not display any peak in the visible region, no ligand field absorptions band was observed,
therefore the bands appeared in the spectra of complexes could be attributed to charge transfer transitions [15,
24]. The electronic spectra of d10 [Zn(II) ,Cd(II) and Hg(II)] complex shows absorption bands at range (2659537313) cm-1, attributed to the MLCT (metal to ligand charge transfer) transition, which are compatible with
those complexes that have the octahedral structure [23,25].
36
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Table (5 ): Electronic Spectral data, magnetic moment of the studied Complexes and two ligands
Antibacterial Activities
The ligands and synthesized metal complexes were screened for their antimicrobial activity by well plate
method in nutrient agar. The activities were expressed in terms of millimeter (mm) by measuring inhibition zone
diameters.( IZ) and compared with the standard DMSO
(as control) . [24-26]. Table (6) and Scheme (4) reveal that the synthesized compounds were potent as
bacteriostatic agents. The plates were incubated in incubator at 37C for 24 hours.. In order to ensure that solvent
had no effect on bacteria, a control test was performed with DMSO and found inactive in culture medium.
[26,27] .Trimethoprim showed activity against E-coli, S. aureus and Bacillus with 4. 5 and 10 mm zones of
inhibition respectively, while L-proline exhibit activity, against all bacterial used, which suggests that Lproline is more active than trimethoprim .Cd (II) and Hg (II) complexes exhibited a broad spectrum
antimicrobial activity as they are active against all selected bacterial isolates. They have also shown a stronger
antibacterial activity than the free ligands as well as the DMSO( as control).The investigation of antibacterial
screening data revealed that most of the synthesized complexes were found to possess various antimicrobial
activities toward Bacillus microorganism. On chelation, the ligand with the N and O donor system might have
inhibited enzyme production, since enzyme which requires a free OH group for their activity appear to be
especially susceptible to deactivation by the ions of the complexes. The chelation also reduces the polarity of
central metal ion because of partial sharing its + ve charge with the donor group and possible electron
delocalization within the whole chelate ring. [27].The other factors like solubility and bond length between the
metal and ligand may also increase the activity [28].
37
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38
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2012, 4(9):4141-4148.
[6] RaheemTaher Mahdi, Taghreed H. Al-Noor, and Ahmed H. Ismael . Journal of Chemical and
Pharmaceutical Research, 2014, 6(5):1286-1294 .
[7] Taghreed H. Al- Noor , Raheem Taher Mahdi , Ahmed .H. Ismail,Preparation,.,Advances in Physics
Theories and Applications ,2012;9 ,pp 1-13
[8] Sangeeta Jain,Sheela Longia,V.K. Ramnani, Peoples Journal of Scientific Research, .(2009).Vol.2(1), Jan
9 ,pp 37-40.
[9]Sakurai H, Kojima Y, Yoshikawa Y, Kawabe K, Yasui H Coordination Chemistry Reviews, 2002; 226 : 187198.
[10] Orvig C, Abrams MJ: Medicinal inorganic chemistry:introduction. Chemical Reviews, 1999;99:2201-2204.
[11] Sorenson, J.R.J. (1982) Metal Ions in Biological Systems (H. Sigel, Ed.), M. Dekker, New York, Vol. 14,
pp. 77-124.
[12]Omoruyi G. Idemudia1*, Peter A. Ajibade1 and Anthony I. Okoh, African Journal of Biotechnology Vol.
11(39), pp. 9323-9329, 15 May, 2012
[13]Geary, W. J.(1971)The Use of Conductivity Measurements in Organic Solvents for the Characterization of
Coordination Compounds.Coord. Chem. Rev., 7, 81-122.
[14] Vogel AIA "Text Book of Quantitative Inorganic Analysis " 2nd Ed (Longman, London). 1978; 694.
[15] Raman, N.; Raja, Y.P.; Kulandaisary, A., Indian Academy of Sc.,( 2001), 113(3),183.
[16] Lin-Vien, D., N.B. Colthup, W.G. Fateley & J.C. Grasselli (1991) The Handbook of Infrared and Raman
Characteristic Frequencies of Organic Molecules Academic Press; San Diego.
[17] Smith, B. (1999) Infrared Spectral InterpretationCRC-Press; Boca Raton.
[18]Nakamoto K. (1997) Infrared and Raman Spectra of Inorganic and Coordination Compounds,5th Edit.,
Part B, Wiley, New York.
[19] Zelenk, V., Z. Vargov & K. Gyryov (2007) Spectrochim. Acta A66: 262-72.
[20] William, K. (1991) Organic Spectroscopy , 3rd edition, Macmillan Education Ltd, London,49-54, 60-75.
[21] Peter A. Ajibade and Omoruyi G.Idemudia, Bioinorganic Chemistry and Applications Volume 2013 (2013),
1- 8
[22] Toyssie P, Charette JJ (1963).. Spectrochim. Acta. 19: 1407-1423.
[23] Shriver. D.W, Atkins P.W. Inorganic Chemistry,2006; 4th Ed., Freeman, New York
[24] Lever, A.B.P. (1984) Inorganic ElectronicSpectroscopy, 2nd Edit., Elsevier, Amsterdam.
[25] Taghreed . H. Al-Noor , Khalid F Ali , Amer J. Jarad and aliea. S .kindeel, Chemistry and Materials 2013;
3(3), 126-139 .
[26]Davidson, I., and Henry, J.B., Clinical Diagnosis by Laboratory Methods, W.B. Saunders Co., Philadelphia,
1974; p. 848.
[27] Tweedy , BG. J. Phytopathology. 1964 ; 55, 910914.
[28] Subhasish S., Dharumadurai D., Sarvanan C., Annamalai P., Physics, Chemistry and Technology, 7(1); 7380, (2009).
39
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